EP0775107B1 - Preparation of o-(2-hydroxyalkyl) oximes - Google Patents
Preparation of o-(2-hydroxyalkyl) oximes Download PDFInfo
- Publication number
- EP0775107B1 EP0775107B1 EP95930419A EP95930419A EP0775107B1 EP 0775107 B1 EP0775107 B1 EP 0775107B1 EP 95930419 A EP95930419 A EP 95930419A EP 95930419 A EP95930419 A EP 95930419A EP 0775107 B1 EP0775107 B1 EP 0775107B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxime
- ketoxime
- catalyst
- carbonate
- salts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000002923 oximes Chemical class 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 22
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkali metal salts Chemical class 0.000 claims description 9
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000004714 phosphonium salts Chemical class 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 3
- 150000002891 organic anions Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 claims 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000011814 protection agent Substances 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 150000003512 tertiary amines Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical class CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 0 CC(CCC*)=NO Chemical compound CC(CCC*)=NO 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MGZDDCVCLLEWOR-UHFFFAOYSA-N acetic acid;tributylphosphane Chemical compound CC(O)=O.CCCCP(CCCC)CCCC MGZDDCVCLLEWOR-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical class [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/54—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
Definitions
- the present invention relates to a process for the preparation of O-(2-hydroxyalkyl)oximes of the general formula I in which R 1 and R 2 each stand for an alkyl group having from 1 to 10 carbon atoms, or form, together with the carbon atom to which they are attached, a 5-membered to 7-membered cycloalkyl radical, and R 3 denotes an alkyl group having from 1 to 10 carbon atoms.
- O-(2-hydroxyalkyl)oximes have great significance as intermediates for plant protectants (cf eg, the prior German Application DE-A 44 15 887).
- aldoximes and ketoximes with unsubstituted or C 1 -C 8 -alkyl-substituted ethylene or propylene carbonate can be hydroxyalkylated in the presence of catalytic amounts of an N-alkylated, stable organic base or of pyridine substituted by a secondary amine.
- Preferred process products I are those which can be produced by this process variant those are preferred in which R 1 and R 2 stand for C 1 -C 4 alkyl groups and primarily C 1 -C 3 alkyl groups or form, together with the carbon atom to which they are attached, a cyclopentyl or cyclohexyl ring, and in particular those in which R 1 and R 2 stand for methyl and/or ethyl or form, together with the carbon atom to which they are attached, cyclohexyl.
- R 3 preferably stands for a C 1 -C 4 alkyl group, particularly for ethyl and more particularly for methyl.
- Most particularly preferred compounds I are those in which R 1 , R 2 and R 3 stand for methyl.
- ketoximes II are generally known or are obtainable by known methods, for example, by the reaction of the corresponding ketones with hydroxylamine.
- the carbonates III are also generally known or can be produced by known methods (cf. eg, EP-A 543,249).
- the molar ratio of carbonate III to ketoxime II is usually from 1:1 to 10:1 and in particular from 4:1 to 7:1.
- Suitable catalysts used either alone or in the form of a mixture, are
- Preferred catalysts are those which are mentioned under ( ⁇ ) and ( ⁇ ).
- the potassium salts are preferably used, especially potassium fluoride or potassium hydrogen carbonate.
- the catalyst primarily the inorganic alkali metal salts and the alkali metal salts of carboxylic acids, can be bonded to a support, if desired.
- suitable supports are aluminum oxide, silica gel, and kieselguhr.
- the amount of catalyst in these supported catalysts is usually from 10 to 50 wt%.
- the catalysts are usually employed in an amount of from 5 to 50 mol%, preferably from 5 to 30 mol%, and more preferably from 5 to 10 mol%, based on the ketoxime II.
- the reaction can be carried out in a single, preferably aprotic, organic solvent or in a solvent mixture. However, the process is preferably carried out without the use of a solvent, in which case an excess of the carbonate III can, in particular, serve as reaction medium.
- Suitable solvents are for example alkylbenzenes, such as, in particular, toluene and also the xylenes, furthermore dialkylketones such as methyl ethyl ketone, halobenzenes such as chlorobenzene, and ethers such as 1,4-dioxane.
- the amount of solvent used is usually from 1 to 9 times and in particular from 2 to 7 times the weight of the ketoxime II. lf the amount of solvent exceeds 9 times the weight of the ketoxime II, conversion and yield usually fall.
- the reaction is preferably carried out at temperatures of from 80°C to 150°C and mostly from 100°C to 140°C and pressures of from 0.5 to 1 bar and especially under standard pressure.
- phase transfer catalyst usually leads to an increase in reaction rate and conversion. However, for simple processing, it is preferred not to use a phase transfer catalyst.
- phase transfer catalysts are quaternary ammonium or phosphonium salts, preferably tetraalkylammonium, tetraalkylphosphonium, trialkylbenzylammonium, or trialkylbenzylphosphonium salts, especially triethylammonium, tributylbenzylammonium, and tetrabutylammonium chlorides, bromides, and hydrogen sulfates, and also tributylhexaphosphonium bromide.
- quaternary ammonium or phosphonium salts preferably tetraalkylammonium, tetraalkylphosphonium, trialkylbenzylammonium, or trialkylbenzylphosphonium salts, especially triethylammonium, tributylbenzylammonium, and tetrabutylammonium chlorides, bromides, and hydrogen sulfates, and also tributylhexaphospho
- the phase transfer catalyst is usually employed in an amount of from 0.5 to 2 mol% and preferably from 0.7 to 1 mol%, based on the ketoxime II.
- the reaction can be carried out batchwise or, preferably, continuously.
- reaction times are normally from 8 to 24 h but mostly from 8 to 16 h.
- reaction product I takes place by methods known per se, preferably by distillation.
- the distillation residues of the crude mixture contain substantially unconverted carbonate III and the catalyst.
- the process is carried out by replenishing the ketoxime II and the carbonate III at a rate equal to the rate of consumption thereof, following the destillation of the product I from the reaction mixture, and the reaction is then repeated.
- the reaction frequently also produces, as by-product, the regio-isomeric compound Ia which is usually obtained in amounts of up to 10 %, based on I.
- the two isomeric compounds I and Ia are normally the first overheads occurring during distillation of the crude product. lf desired, the isomer Ia can be substantially separated from the compound I by methods known per se, preferably by fractional distillation.
- the end products I are important intermediates for crop protection agents, especially for herbicides of the cyclohexenone type (cf. DE-A 44 15 887).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Medicinal Preparation (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4427289 | 1994-08-02 | ||
| DE4427289 | 1994-08-02 | ||
| PCT/EP1995/003001 WO1996004238A1 (en) | 1994-08-02 | 1995-07-28 | Preparation of o-(2-hydroxyalkyl) oximes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0775107A1 EP0775107A1 (en) | 1997-05-28 |
| EP0775107B1 true EP0775107B1 (en) | 1999-10-13 |
Family
ID=6524699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95930419A Expired - Lifetime EP0775107B1 (en) | 1994-08-02 | 1995-07-28 | Preparation of o-(2-hydroxyalkyl) oximes |
Country Status (17)
| Country | Link |
|---|---|
| EP (1) | EP0775107B1 (enExample) |
| JP (1) | JP4017022B2 (enExample) |
| KR (1) | KR100388882B1 (enExample) |
| CN (1) | CN1086383C (enExample) |
| AT (1) | ATE185553T1 (enExample) |
| AU (1) | AU3381395A (enExample) |
| BR (1) | BR9508498A (enExample) |
| CA (1) | CA2196452A1 (enExample) |
| DE (1) | DE69512786T2 (enExample) |
| DK (1) | DK0775107T3 (enExample) |
| ES (1) | ES2139935T3 (enExample) |
| GR (1) | GR3031531T3 (enExample) |
| HU (1) | HU216742B (enExample) |
| IL (1) | IL114776A (enExample) |
| MX (1) | MX9700809A (enExample) |
| WO (1) | WO1996004238A1 (enExample) |
| ZA (1) | ZA956402B (enExample) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078710A1 (en) * | 1999-06-23 | 2000-12-28 | Alliedsignal Inc. | Method of making hydroxylamine salts |
| CN107531617B (zh) * | 2015-05-22 | 2020-10-02 | 日产化学工业株式会社 | O-[1-(2-羟基丙基)]肟化合物的制造方法 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3965177A (en) * | 1972-05-03 | 1976-06-22 | Texaco Inc. | Catalytic process |
| US5434306A (en) * | 1993-11-25 | 1995-07-18 | Ciba-Geigy Corporation | Process for the preparation of O-substituted oximes |
-
1995
- 1995-07-28 BR BR9508498A patent/BR9508498A/pt not_active IP Right Cessation
- 1995-07-28 JP JP50618096A patent/JP4017022B2/ja not_active Expired - Lifetime
- 1995-07-28 MX MX9700809A patent/MX9700809A/es not_active IP Right Cessation
- 1995-07-28 AT AT95930419T patent/ATE185553T1/de active
- 1995-07-28 HU HU9700313A patent/HU216742B/hu not_active IP Right Cessation
- 1995-07-28 DK DK95930419T patent/DK0775107T3/da active
- 1995-07-28 EP EP95930419A patent/EP0775107B1/en not_active Expired - Lifetime
- 1995-07-28 AU AU33813/95A patent/AU3381395A/en not_active Abandoned
- 1995-07-28 KR KR1019970700696A patent/KR100388882B1/ko not_active Expired - Lifetime
- 1995-07-28 CN CN95194843A patent/CN1086383C/zh not_active Expired - Lifetime
- 1995-07-28 ES ES95930419T patent/ES2139935T3/es not_active Expired - Lifetime
- 1995-07-28 WO PCT/EP1995/003001 patent/WO1996004238A1/en not_active Ceased
- 1995-07-28 DE DE69512786T patent/DE69512786T2/de not_active Expired - Lifetime
- 1995-07-28 IL IL11477695A patent/IL114776A/xx not_active IP Right Cessation
- 1995-07-28 CA CA002196452A patent/CA2196452A1/en not_active Abandoned
- 1995-08-01 ZA ZA9506402A patent/ZA956402B/xx unknown
-
1999
- 1999-10-14 GR GR990402548T patent/GR3031531T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUT77753A (hu) | 1998-07-28 |
| HU216742B (hu) | 1999-08-30 |
| WO1996004238A1 (en) | 1996-02-15 |
| DE69512786T2 (de) | 2000-03-02 |
| KR100388882B1 (ko) | 2004-03-31 |
| JP4017022B2 (ja) | 2007-12-05 |
| ZA956402B (en) | 1997-02-03 |
| MX9700809A (es) | 1997-05-31 |
| KR970704671A (ko) | 1997-09-06 |
| CA2196452A1 (en) | 1996-02-15 |
| ES2139935T3 (es) | 2000-02-16 |
| CN1156445A (zh) | 1997-08-06 |
| AU3381395A (en) | 1996-03-04 |
| DK0775107T3 (da) | 1999-12-27 |
| EP0775107A1 (en) | 1997-05-28 |
| BR9508498A (pt) | 1997-12-30 |
| CN1086383C (zh) | 2002-06-19 |
| JPH10506617A (ja) | 1998-06-30 |
| IL114776A (en) | 2000-11-21 |
| GR3031531T3 (en) | 2000-01-31 |
| ATE185553T1 (de) | 1999-10-15 |
| IL114776A0 (en) | 1995-11-27 |
| DE69512786D1 (de) | 1999-11-18 |
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